Virginia Gov. Robert R. McDonnell speaks at the Bloomberg Link Economic Summit in Washington on April 30. (Andrew Harrer/Bloomberg)

Virginia Gov. Robert F. McDonnell welcomed the nation’s governors to Williamsburg for the annual meeting of the National Governors Association last July.

At the historic executive mansion in Richmond, McDonnell’s wife, Maureen, hosted a lunch for the governors’ spouses. To welcome the crowd to Virginia, Maureen McDonnell distributed a gift bag with unique products from around the state, such as a wine coaster and stopper from a Colonial Williamsburg silver shop and a champagne flute from the Trump Winery in Charlottesville.

Also included in the gift bags were samples of Anatabloc, a dietary supplement containing a chemical found in tobacco that is manufactured by Star Scientific, the company whose chief executive paid the $15,000 catering bill at the wedding of the McDonnells’ daughter and whose ties with the first family are now the subject of an FBI inquiry.

As the FBI and the Virginia State Police try to determine whether the Republican governor improperly helped Star or its chief executive, Jonnie R. Williams Sr., in exchange for the catering or other gifts, details of the first family’s relationship with the company continue to emerge.

The inclusion of Anatabloc in the gift bags offers a new example of the McDonnells’ work to promote the company, which took place as Star and its chief executive provided more than $120,000 in publicly disclosed gifts and campaign donations to McDonnell, his campaign and his political action committee.

Previous Washington Post coverage of Gov. Bob McDonnell and ties to Star Scientific.

In addition, documents newly obtained by The Washington Post through the Freedom of Information Act also show that Maureen McDonnell was in close contact with Williams in 2011 and 2012.

She frequently invited Williams to charitable and political events, including a 2011 fundraising reception with Republican presidential candidate Mitt Romney.

Last year, Williams suggested a long list of Richmond-area doctors who he thought should be included at an event at the governor’s mansion bringing together health-care leaders and state lawmakers. More than half made the list of invitees.

McDonnell said recently that Star Scientific has received no preferential treatment from state officials, noting that the company has not received state economic incentives or financial grants during his time in office.

“I think it’s important for the people of Virginia to know nothing has been done with regard to my relationship with Mr. Williams or his company, Star Scientific, to give any kind of special benefits to him or his company,” he said on WTOP radio’s “Ask the Governor” program.

Williams’s lawyer, Jerry Kilgore, declined to comment.

McDonnell spokesman Tucker Martin said the Anatabloc samples were included in the gift bags to represent one of Maureen McDonnell’s focus areas as first lady — “preventative health care and wellness.” He also noted that the company is headquartered in Glen Allen, near Richmond.

Martin did not respond to a question about who paid for the Anatabloc samples.

The other gifts represented her attempts to promote the Virginia wine industry, the spokesman said.

McDonnell has said Williams is a friend who paid for the wedding food as a gift to his daughter. McDonnell did not disclose the gift, citing Virginia law that requires only elected officials and not members of their immediate families to annually disclose gifts.

McDonnell has not answered questions about whether Williams provided members of his family with any other gifts. People familiar with the FBI and state police interviews have said investigators are asking questions about the wedding but are also interested in other gifts Williams provided to Maureen McDonnell.

Some of the couples’ other efforts to promote the company are already known. Maureen McDonnell flew to Florida three days before her daughter’s 2011 wedding, where she spoke at a gathering of doctors and investors interested in learning more about anatabine, the key chemical found in Anatabloc.

In a brief speech, attendees said, she told the crowd that she supported the product and believed it could be used to lower health-care costs in Virginia.

In August 2011, the governor and first lady attended a luncheon at the executive mansion that marked the formal launch of Anatabloc, an anti-inflammatory dietary supplement that does not require approval by the U.S. Food and Drug Administration.

Star Scientific, a former tobacco company, later began selling a skin-cream version of the supplement as well as tablets.

McDonnell’s spokesman has said the mansion event was hosted by the first lady and paid for by the governor’s political action committee. The spokesman said the governor stopped by to acknowledge research grants Star Scientific was awarding to public medical schools.

A picture of McDonnell holding up a package of Anatabloc was featured on the product’s Facebook page. The spokesman has said its use was unauthorized, and it has been removed.

But the governor’s spokesman has refused to answer questions about other Star Scientific events the McDonnells might have attended.

For instance, in October 2011, Star Scientific investors advertised that Maureen McDonnell would be the “featured guest” at a cocktails-and-dinner event for Anatabloc at the Westin Richmond hotel.

Martin would not say whether she attended that event, nor two others that same month held in Flint, Mich., and Newport Beach, Calif., where doctors and investors gathered to learn about the product. A travel log maintained by the Virginia State Police’s executive protection unit, however, shows that a member of the first couple was in Flint on Oct. 22, the same day as the Star event there. Gov. McDonnell’s calendar shows he was in Washington that day. Martin said Maureen McDonnell “customarily” travels with a state police detail, although not always.

Martin would say only that Maureen McDonnell has “appeared at hundreds of events for issues and causes” that she has chosen to advocate. He said none of those trips involved state expenses except for the state police when they traveled with her.

A Star Scientific spokesman would not say whether Maureen McDonnell attended the Star events in Richmond, Michigan and California.

“Our company neither sought nor received any special benefits from any public official and was glad to be part of any effort to promote business and create jobs in the Commonwealth of Virginia,” Talhia T. Tuck, vice president for communications and investor relations, said in a statement.

But the new documents reveal that Maureen McDonnell reached out to Williams on several occasions about her projects.

The documents were obtained in response to a Freedom of Information Act request for communications between various state employees and Star workers. While a handful of e-mails were released in response to the request, a McDonnell lawyer indicated that 10 others were withheld from the public because they were considered “working papers” of the governor or because they were “not prepared for or used in the transaction of public business.”

In September 2011, Maureen McDonnell e-mailed Williams to invite him and his wife, Celeste, to a fashion show to benefit the American Cancer Society.

A year later, she e-mailed an invitation to a Republican Governors Association golf outing featuring Donald Trump. In December 2011, she sent Williams an invitation to a Romney fundraising reception at a Richmond hotel.

“Dearest Jonnie — Hope everything is going well for you both, and I look forward to the next time we are able to get together,” Maureen McDonnell wrote to Williams in a May 2012 e-mail before asking him to become a paid sponsor of a coffee-table book she was helping to publish to celebrate the 200th anniversary of the governor’s mansion.

At the February 2012 event for the health-care industry at the governors mansion, 21 of the 38 doctors who Williams suggested be invited made the cut, according to an attendance list released by the governor’s office, including one who had recorded a radio ad in the Richmond area for Anatabloc.

In addition, four Star Scientific employees — including Williams and son Jonnie Williams Jr. — attended the event. Two other scientists who have been paid consultants to Star’s scientific research also made the list.

Star was the only private company to send so many employees to the reception, which mostly included hospital executives and state lawmakers.

The governor’s spokesman said the health-care event was “similar to dozens of other events” held for leaders in various industries and that it was not unusual that Williams was asked to suggest possible attendees.

“Stakeholders are regularly asked for input in regard to who is invited to such events,” Martin said.

Del. Robert H. Brink, an Arlington Democrat who sits on the key health subcommittee of the powerful Appropriations Committee, was also there. He said the event provided attendees a rare opportunity to mingle in a social setting with lawmakers during the legislative session.

“It’s certainly useful,” he said of an invitation to such an event for a company. “It gives representatives of private companies a chance for face time with members of the General Assembly. And the smaller the number, the more distinctive they are.”

Alice Crites and Laura Vozzella contributed to this report.