Former Secretary of State Hillary Rodham Clinton’s emails reveal how prominently the Clinton Foundation factored into her thinking as America’s top diplomat, raising questions about where she drew the line between official business and aiding the family charity run by her husband and daughter.

In one instance, Mrs. Clinton appeared to try to steer a Haiti earthquake recovery project to the foundation, according to new emails released this week as the State Department belatedly complies with open records requests for her communications during her four years in office.

Another email shows Mrs. Clinton directing a State Department employee to handle solicitation of money from Norway for a program she was about to announce in a speech at the Clinton Global Initiative in 2010, and which was being run by the United Nations Foundation, another nonprofit created by Ted Turner that has close ties to her family’s operation.

The State Department late Monday released more than 4,300 emails Mrs. Clinton sent from an account she kept on an email server at her home in New York during her time in office. The release, the fourth and largest batch so far, has drawn scrutiny chiefly for the amount of now-classified information, which was in nearly 3 percent of her messages.

But the emails are also giving a clearer picture of how she handled her job and, in particular, her role as top diplomat, married to a former president who had interests of his own.

In one message, Chelsea Clinton, who was on the ground in Haiti, sent both of her parents her thoughts about U.S. government policy and her father’s role in the rebuild.

At the time, former President Bill Clinton was the U.N.’s special envoy to Haiti for recovery and reconstruction needs.

In another exchange, Mrs. Clinton praised an idea to set up schools in Haiti, developed by David Domenici, longtime domestic partner to top Clinton aide Cheryl Mills, who was her chief of staff at the department.

Ms. Mills, who served as a member of the Clinton Foundation’s board of directors before and after her stint at the State Department under Mrs. Clinton, forwarded the ideas to Mrs. Clinton, who responded enthusiastically.

“Great ideas (no surprise). Let’s work toward solid proposal maybe to Red Cross and Clinton Foundation since they have unencumbered $,” Mrs. Clinton wrote.

The Clinton Foundation didn’t respond to a request for comment Tuesday on the emails or on what became of the proposal. Records show the foundation would become a major player in the relief and reconstruction efforts, raising more than $30 million.

The emails have become a major political problem for Mrs. Clinton, the front-runner for the Democrats’ 2016 presidential nomination.

The Republican National Committee said the real contents of Mrs. Clinton’s emails could be even more damaging.

“But because Clinton deleted more than 30,000 emails and then had her server wiped, we may never fully know the true extent to which she jeopardized our national security or mixed diplomacy with Clinton Foundation fundraising,” the RNC said.

The State Department, meanwhile, has had to defend Mrs. Clinton’s handling of classified material, saying that while more than 180 messages now contain secret information, none of it was marked as secret at the time she handled it.

“It’s very difficult for us, and I said this before, to go back and to judge what the circumstances were at the time this information was shared and to make a judgment on whether that information was classified at the time. It’s not a black-and-white issue,” department spokesman Mark Turner told reporters Tuesday.

As secretary, Mrs. Clinton also had to make special arrangements for how to handle business from the Clinton Foundation, which had interests in many of the same international projects the State Department did.

One of those was the Global Alliance for Clean Cookstoves. Mrs. Clinton announced the public-private partnership in a speech at the Clinton Global Initiative in 2010.

A week or so before the speech, she sent an email to Kris M. Balderston, who served as the secretary’s special representative for global partnerships and managed the departments’ Global Partnership Initiative, instructing him to pursue a contribution from Norway.

“The Norwegian FM told me Norway would join the Alliance and we should coordinate w his UN Rep. Will you pls follow up? Thx.,” wrote Mrs. Clinton.

Mr. Balderston responded to the email three days later: “We spoke to the Norway’s Ambassador to the UN and they are joining the Alliance for Clean Cookstoves for $600,000 the first year. They noted that this is a down payment and would contribute a ‘substantial amount for this endeavor’ in the future. They wanted to move quickly for the CGI announcement and to see a business plan before they commit more.”

“Thnx for making this important call. Other countries including France and Finland were waiting for the Norway signal,” added Mr. Balderston.

The Alliance — a program that replaces wood-fired cookstoves in developing countries with cleaner and more efficient alternatives — is run by the U.N. Foundation, which has donated between $250,000 and $500,000 to the Clinton Foundation.

The government of Norway also is a major donor to the Clinton Foundation, contributing between $10 million and $25 million, according to the foundation.

Kathleen Clark, a law professor at Washington University in St. Louis and an expert on ethics in government, said that having Mrs. Clinton make the announcement at CGI was enough to raise red flags.

“It needs some ethical vetting,” she said. “There are restrictions on government officials. You are not supposed to use governmental power to endorse a specific organization.”

She pointed to federal regulations that spell out potential conflicts of interest that government officials are required to avoid: “An employee shall not use his public office for his own private gain, for the endorsement of any product, service or enterprise, or for the private gain of friends, relatives or persons with whom the employee is affiliated in a nongovernmental capacity, including nonprofit organizations of which the employee is an officer or a member.”

The State Department did not respond to inquiries about whether Mrs. Clinton’s 2010 speech at CGI was vetted by ethics watchdogs.

Yet another email showed Mrs. Clinton negotiating how to deliver a speech on Internet freedom at the D.C.-based Newseum, whose chairman also ran the Knight Foundation, which has financial ties to CGI.

“I spoke w Chairman of the Newseum and there will be no cost for S speech on 21st,” said Alec Ross, a senior adviser to Mrs. Clinton, referring to the secretary as “S.”

“They’re honored to host. The Chair is the CEO of the Knight Foundation and if the event requires sponsorship for it to be free they will sponsor. Whatever our legal regs are, Newseum and/or Knight will accommodate,” he said.

The Knight Foundation, under CEO Alberto Ibarguen, has been a financial supporter of the Clinton Foundation and CGI, including giving between $100,000 and $250,000 to the foundation.

Newseum spokesman Johnathan Thompson confirmed that the museum provided complimentary space for Mrs. Clinton’s speech.

“There’s not a policy per se, but given that this was a major U.S. statement on Internet freedom by the secretary of state, the Newseum waived the room fee,” he said.

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